4-tertiary-catechol-aqueous solution composition

ABSTRACT

A homogeneous 4-tertiary-butyl-catechol aqueous solution composition comprising 4-tertiary-butyl-catechol, water and a saturated hydrocarbon having five or more carbon atoms.

United States Patent Harada et al.

11 1 3,656,980 51 Apr. 18,1972

4-TERTIARY-CATECHOL-AQUEOUS SOLUTION COMPOSITION Inventors: Tetsuya Harada, Chiba; Nobuo Fuzinami, Ichihara; Koichi Hasegawa, Chiba; Akira Shibatani, Ichihara, all of Japan Assignee: Japan Synthetic Rubber Co., Ltd., Tokyo,

Japan Filed: Aug. 10, 1970 Appl, No.: 62,609

Foreign Application Priority Data Aug. 12, 1969 Japan .;....44/63305 U.S. c1 ..106/285, 106/31 1, 252/73, 252/364, 260/666.5

Int. Cl. ..C08h 17/28 Primary Examiner-Julius Frome Assistant Examiner-David A. Jackson Attorney-Sherman and Shalloway [5 7] ABSTRACT A homogeneous 4-tertiary-butyl-catecho] aqueous solution composition comprising 4-tertiary-butyl-catechol, water and a saturated hydrocarbon having five or more carbon 'atoms.

3 Claims, No Drawings 4-TERTIARY-CATECHOL-AQOEOUS SO LUTION COMPOSITION This invention relates to a saturated hydrocarbon-containing 4-tertiary-butyl-catechol aqueous solution composition which is difficulty frozen at low temperatures.

4-Tertiary-butyl-catechol is used broadly as a polymerization inhibitor for many industrially valuable polymerizable monomers during their storage or during polymerization thereof, and as an antioxidant for polyolefins, various plastics, lubricants and the like. Although 4-tertiary-butylcatechol is sometimes used in the powdery or massive form, it is frequently used in the form of an aqueous solution consisting of 85 percent by weight of 4-tertiary-butyl-catechol and 15 pentane, n-hexane, 3-methylpentane, 2,3-dimethylbutan e, n-

heptane, 2-methylhexane, 3-ethylpentane, 2,4-dimethylpentane, n-octane, 2-methylheptane, 2,5-dimethylhexane, 2,4,4- trimethylpentane, n-nonane, n-decane, cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, ethylcyclopentane, l l-dimethylcyclopentane, 1,2-dimethylcyclopentane, cyclooctane, ethylcyclohexane, l,3-dimethylcyclohexane and paramenthane. In this invention it is preferable that the composition is composed of 50 93 percent of 4- tertiary-butyl-catechol, 5 48 percent of water and 2 45 percent of a saturated hydrocarbon, or 0.5 45 percent of 4-tertiary-butyl-catechol, 0.5 percent of water and 50 90 percent of a saturated hydrocarbon. A composition composed of 70 90 percent of 4-tertiary-butyl-catechol, 5 25 percent of percent by weight of water in view of equipment costs, manuwater and 5 25 percent of a saturated hydrocarbon is parfacturing conditions and ease in handling. (The percentile ticularly preferred. ratio is based on weight throughout the specification unless 4-z ni -b h h l, water d a saturated h d otherwise specified.) In the latter case, since 4-tertiary-butylb n a e ell i d t h at room temperature if h C o takes a liquid form, h eighing and transportation position ratio is maintained within the above-mentioned thereof can be conducted very easily, but it possesses one fatal range, and the intended composition can be easily prepared defect in that the solution has a high freezing point such as 6 with good reproducibility in a vessel equipped with a simple -8 and it easily freezes during storage in w1nter. MorB stirrer. Such composition of this invention is advantageous in specifically, at temperatures lower than the freezing point the h f ll ing i t an aging at e t h as i d i SOlUilOn freezes not only when stored in a tank but 3150 while the preparation of the conventional 4-teniary-butyl-catechol. being transported in P t P P P P when it is allowed water mixture is not necessary in the present invention; when to stand during storage, it sometimes happens that the solution compared i h h conventional 4- ni -b h 1 does not freeze at temperatures lower than the freezing point, water mixture System, h composition f hi invention h a but once the solution is moved or transferred, stimulation such very l viscosity at h Same 4 i h 1- h 1 38 frictional contact with a wall causes Solution to centration and therefore, the operability can be imtreezeilth h g the g k l sel'utlel 1t l e 'y proved; and even if the saturated hydrocarbon contained in p t e epetatleh ah uet eetlhg er a ehg tlthe y the com osition of this invention remains in the ol merizameans of a Special heating device tion syst m after the treatment for removal of 4-ter tiai' y-butylth Order to lower the freezing point it has been P p to catechol, it does not adversely affect the polymerization reac- P P f an aqueous Solution from 'y' y e tion. Accordingly, the composition of this invention is of great containing small amounts of by-products such as 3-tert1aryindustrial utility butyl-catechol and di-tertiary-butyl-catechol. However, since This invention i now be d il d b f i g to examthese y'h e fhtfieultly removed eVeh by Washmg ples. Since the 4-tertiary-butyl-catechol aqueous solution Wlth alkalls, the h g y'p Bt bad lhflhehees to compositions exhibit a temperature-time curve comprising Subsequent epetatleh Steps and Propetttes of e Products, 4() temperature lowering-super cooling-temperature risinge h y Such method oflowetlhg the heel plateau, the stability of the composition is evaluated based on 2 Pelht hot PP P the freezing point in each example.

The primary object of this invention IS to provide a homogeneous 4-tertiary-butyl-catechol aqueous solution com- EXAMPLE 1 osition which is free of the above-mentioned defects, namely g 4-tertiary-butyl-catechol aqueous solution composition A g i g t q of zgg weight g which has a low freezing point and retains the original catec a pgumy 0 F e g i I e polymerization-inhibiting and oxidation-preventing activities Same g percim im i'g mixture of 4-tertiary-butyl-catechol, whereby automatic weighing and g p f 3 g y i to g transportation, to which great importance has been attached y g t 0 t? ypemaneb f' y z in the art, can be easily accomplished even in winter. met y pentane an 8 perqem y welght 0 mg y open The above object of this invention can be attained by adding time) and 21 percent by we'ght of Water was mnmfnely to a mixture system comprising water and 4 temary butyl to thereby form an aqueous solution composition having a catechol a saturated hydrocarbon as a third component which freezmg polm f e the P V allowed to does not adversely affect the utility of 4 tertiary butyl stand or under similar conditions, the composition was stable catechol. Generally, saturated hydrocarbons are immiscible at-IO for more than lodays' with water and form a separate phase when admixed therewith, but it has been unexpectedly found that, in the EXAMPLES2 16 system comprising water, 4tertlary-butyl catechol and a satu- 4Tertlary-butyl catechol, water and a saturated hydrocarrated hydrocarbon according to thlsinventlon, they are bon as ind cated In Table 1 were mixed together m the same uniformly admixetllalwith one another and the resulting commtg-n1? asf in Example lt.SThfe :grxmg rzlttt os of the components osition 1S ver sta e. an e reezing porn 0 e resu mg compost ions are p Saturated h ydrocarbons having five or more carbon atoms, shown in Table 1. Each of the resulting composition was stable especially up to 10 carbon atoms are preferably used in this inat -l0 C. for more than 10 days when kept at rest or in a vention. As such saturated hydrocarbon there may be cited nsimilar state.

TABLE 1 4-teii')tlatr3i'- Saturated hydrocarbon eatetzliol Water Amount (Percent (Percent (Percent Freezing y b by point Example No. weight) weight) weight) Kind C.)

12.5 12.5 Cyclohexane -1.7 22 g 1% 2,4,4-trimethypentane :2 15 2 83 Hexane mixture same as used in Example 1. 0 15 2 83 n-Nonane 1 88 5 6 n-Decane 1 TABLE l-(ontinucd 4-tertiary- Saturated hydrocarbon butyloateehol Water Amount (Percent (Percent (Percent Freezing by y by point Example No. weight) weight) weight) Kind C.)

72 23 n-Pentane 1.5 72 7 21 Cyclopentane 2 79 5 16 n-Hexane. -1 42 2 56 n-Nonane -1 62 24 14 Methycyclohexane 1 56 34 Cyclohexane .4 1 34 4 62 2,4,4-trlmcthylpentane. 0 25 4 71 n-Nonane t t t o o o H 0 10 3 87 3-methylpentanc i t a t t t t t 4 i t t. 1

What we claim I and 50 90 percent by weight of a saturated hydrocarbon hav- 1. A homogeneous 4-tertiary-butyl-catechol aqueous mixg five to 10 Carbon atomsture consisting essentially of 50 93 percent by weight of 4- A homogeneous 4-tomafY-butyl'oatoohol aqueous tertiary-butyl-catechol, 5 48 percent by weight of water a d ture consisting essentially of 70 90 percent by weight of 4- 2 45 percent by weight of a atu ated hyd a b h i tertlary-butyl-catechol, 5 25 percent by weight of water and five to 10 carbon atoms. 5 percent by weight of a saturated hydrocarbon having 2. A homogeneous 4-tertiary-butyl-catechol aqueous mixfive I0 10 Carbon ms. ture consisting essentially of 0.5 45 percent by weight of 4- tertiary-butyl-catechol, 0.5 l0 percent by weight of water 

2. A homogeneous 4-tertiary-butyl-catechol aqueous mixture consisting essentially of 0.5 - 45 percent by weight of 4-tertiary-butyl-catechol, 0.5 - 10 percent by weight of water and 50 - 90 percent by weight of a saturated hydrocarbon having five to 10 carbon atoms.
 3. A homogeneous 4-tertiary-butyl-catechol aqueous mixture consisting essentially of 70 - 90 percent by weight of 4-tertiary-butyl-catechol, 5 - 25 percent by weight of water and 5 - 25 percent by weight of a saturated hydrocarbon having five to 10 carbon atoms. 